Polycarbonate from 4,4&#39;-bis (4-hydroxyphenyl thio)biphenyls

ABSTRACT

The present invention relates to the novel monomer 4,4&#39;-bis(4-hydroxyphenyl thio)biphenyl, to a process for its production and to its use in the preparation of polycarbonates, polyurethanes, polyesters, polysulfones and polyethers which polymer resins are useful in the preparation of films, fibers and molded parts.

FIELD OF THE INVENTION

This invention is directed to monomers and more particularly to4,4'-bis(4-hydroxyphenyl thio)biphenyls.

SUMMARY OF THE INVENTION

The present invention is directed to novel monomers identified as4,4'-bis(4-hydroxyphenyl thio)biphenyls of the structural formula##STR1## wherein R₁, R₂, R₃ and R₄, which may be the same or different,are C₁ -C₄ -alkyl, Cl or Br, and n₁, n₂, n₃ and n₄, which may be thesame or different, are 0, 1, or 2, as well as to a process for theirsynthesis and their use in the preparation of certain polymeric resins.

DETAILED DESCRIPTION OF THE INVENTION

A route suitable for the synthesis of the generic4,4'-bis(4-hydroxyphenyl thio)bisphenyls is illustrated by the followinggeneral reaction scheme for the synthesis of 4,4'-bis(4-hydroxyphenylthio)biphenyl, the preferred monomer of the present invention: ##STR2##As indicated in the above reaction scheme, 4,4'-dibromobiphenyl isreacted with 4-mercaptophenol in the presence of potassium carbonate anddimethylformamide to produce the 4,4'-bis(4-hydroxyphenyl thio)biphenylof the present invention. The resulting monomer is recovered as aprecipitate and is then separated and dried.

The generic 4,4'-bis(4-hydroxyphenyl thio)biphenyls of the invention areuseful as monomers or as one of the comonomers in the synthesis ofpolycarbonates, polyurethanes, polyesters, polysulfones, polyethers andother polymers. The corresponding comonomer in the synthesis ofcopolycarbonates may be a dihydric phenol selected from the groupconsisting of 2,2-bis(4-hydroxyphenyl)-propane (bisphenol A);2,4'-dihydroxydiphenylmethane; bis-(2-hydroxyphenyl)-methane;bis-(4-hydroxyphenyl)-methane; bis-(4-hydroxy-5-nitrophenyl)-methane;bis-(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)-methane;1,1-bis(4-hydroxyphenyl)-ethane; 1,2-bis-(4-hydroxyphenyl)-ethane;1,1-bis-(4-hydroxy-2-chlorophenyl)-ethane;1,1-bis-(2,5-dimethyl-4-hydroxyphenyl)-ethane;1,3-bis-(3-methyl-4-hydroxyphenyl)-propane;2,2-bis-(3-phenyl-4-hydroxyphenyl)-propane;2,2-bis-(3-isopropyl-4-hydroxyphenyl)-propane;2,2-bis-(4-hydroxynaphthyl)-propane; 2,2-bis-(4-hydroxyphenyl)-pentane;3,3-bis-(4-hydroxyphenyl)-pentane; 2,2-bis-(4-hydroxyphenyl)-heptane;bis-(4-hydroxy;henyl)-phenylmethane;bis-(4-hydroxyphenyl)-cyclohexylmethane;1,2-bis-(4-hydroxyphenyl)-12-bis-(phenyl)-ethane;2,2-bis-(4-hydroxyphenyl)-1,3-bis-(phenyl)-propane; and2,2-bis-(4-hydroxyphenyl)-1-phenylpropane. Such polymers are generallyuseful in films, fibers, injection molded parts, extruded parts andmolded parts, blow molded articles and coatings.

Such polycarbonates are produced using the novel monomers of theinvention by well-known methods, such as disclosed in U.S. Pat. Nos.2,964,794; 2,970,131; 2,991,237; 2,999,835; 2,999,846; 3,028,365;3,153,008; 3,187,065; 3,215,668; and 3,248,414, all incorporated hereinby reference and in the monograph H. Schnell, Chemistry and Physics ofPolycarbonates, Interscience Publishers, New York, N.Y., 1964.Preferably, such polycarbonates may be produced by the well-known meltpolymerization technique taught in the above references.

Such polyurethanes are produced using the novel monomers of theinvention by well-known methods, such as disclosed in U.S. Pat. Nos.2,266,777; 2,284,637; 2,284,296; 2,511,544, all incorporated herein byreference and in the text Polyurethanes: Chemistry and Technology, Vol.1, J. H. Saunders and K. C. Frisch, Interscience Publishers, New York,N.Y., 1964.

Such polyesters are produced using the novel monomers of the inventionby well-known methods, such as disclosed in U.S. Pat. Nos. 2,980,650;3,185,668; 3,185,670 and 3,268,482, all incorporated herein byreference, and in the text Polyesters (two parts), edited by Norman G.Gaylord, Interscience Publishers, New York, 1962.

Such polysulfones are produced using the novel monomers of the inventionby well-known methods, such as disclosed in U.S. Pat. Nos. 3,236,808;3,236,809; 3,409,599 and 3,742,087, all incorporated herein byreference.

Such polyethers are produced using the novel monomers of the inventionby well-known methods, such as disclosed in U.S. Pat. Nos. 1,922,459;2,253,723; 2,991,313 and 3,651,151, all incorporated herein byreference, and in the text Polyethers (three parts), edited by Norman G.Gaylord, Interscience Publishers, New York, 1962.

The invention will further be illustrated, but is not intended to belimited, by the following example.

EXAMPLE Preparation of 4,4'-dibromobiphenyl

Biphenyl (15.4 g, 0.10 mol), bromine (21.8 ml, 0.40 mol) and 200 ml ofglacial acetic acid were placed in a flask equipped with a stirrer,heating mantle, and condenser and refluxed for 17 hours. The reactionmixture was cooled to 20°-25° C. and a white solid collected, washedwith water and air dried to yield 24.5 g (79% yield) of4,4'-dibromobiphenyl (mp 162°-165° C.).

Preparation of 4,4'-bis(4-hydroxyphenyl thio)biphenyl (HPSB)

Potassium carbonate (75.9 g, 0.55 mol) was charged to a 2 liter flaskequipped with a stirrer, condenser, dropping funnel, thermometer andnitrogen purge. Dimethylformamide (200 ml) was added and the solutionheated to 80°-90° C. 4-mercaptophenol (69.3 g, 0.55 mol) in 200 ml ofdimethylformamide was added to the stirred reaction mixture over onehour. The reaction mixture was maintained at 100°-110° C. for two hours.Solid 4,4'-dibromobiphenyl (78 g, 0.25 mol) was then added over onehour. The reaction mixture was refluxed for 18 hours, cooled to roomtemperature, and poured into 10% HCl. The white to yellow solid wascollected with suction and washed with water. The solid was treated with5-10% NaOH and filtered once more with suction. The mother liquor wasacidified to pH≈2 and the solid collected and recrystallized fromchlorobenzene/methanol. A 34% yield of pure HPSB was obtained having amelting point of 214°-217° C.

Analysis of C₂₄ H₁₈ O₂ S₂ (%)--Calculated: C, 71.64; H, 4.47; S, 15.92.Determined: C, 71.76; H, 4.61; S, 15.73.

Although the invention has been described in detail in the foregoing forthe purpose of illustration, it is to be understood that such detail issolely for that purpose and that variations can be made therein by thoseskilled in the art without departing from the spirit and scope of theinvention except as it may be limited by the claims.

What is claimed is:
 1. A process for preparing an aromatic copolycarbonate resin comprising reacting a monomer of the structural formula ##STR3## wherein R₁, R₂, R₃ and R₄ independently are C₁ -C₄ -alkyl, chlorine or bromine and n₁, n₂, n₃ and n₄, independently are 0, 1 or 2, with a member selected from the group consisting of carbonyl bromide, phosgene, bischloroformic ester of said monomer and diaryl carbonate.
 2. A process for preparing an aromatic copolycarbonate resin comprising reacting a comonomer of the structural formula ##STR4## wherein R₁ -R₄ independently are C₁ -C₄ alkyl, chlorine or bromine and n₁ -n₄ independently are 0, 1 or 2 with at least one dihydric phenol selected from the group consisting of 2,2-bis(4-hydroxyphenyl)-propane (bisphenol A); 2,4'-dihydroxydiphenylmethane; bis-(2-hydroxyphenyl)-methane; bis-(4-hydroxyphenyl)-methane; bis-(4-hydroxy-5-nitrophenyl)-methane; bis-(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)-methane; 1,1-bis(4-hydroxyphenyl)-ethane; 1,2-bis-(4-hydroxyphenyl)-ethane; 1,1-bis-(4-hydroxy-2-chlorophenyl)-ethane; 1,1-bis-(2,5-dimethyl-4-hydroxyphenyl)-ethane; 1,3-bis-(3-methyl-4-hydroxyphenyl)-propane; 2,2-bis-(3-phenyl-4-hydroxyphenyl)-propane; 2,2-bis-(3-isopropyl-4-hydroxyphenyl)-propane; 2,2-bis-(4-hydroxynaphthyl)-propane; 2,2-bis-(4-hydroxyphenyl)-pentane; 3,3-bis-(4-hydroxyphenyl)-pentane; 2,2-bis-(4-hydroxyphenyl)-heptane; bis-(4-hydroxy;henyl)-phenylmethane; bis-(4-hydroxyphenyl)-cyclohexylmethane; 1,2-bis-(4-hydroxyphenyl)-2,3-bis-(phenyl)-ethane; 2,2-bis-(4-hydroxyphenyl)-1,2-bis-(phenyl)-ethane; and 2,2-bis-(4-hydroxyphenyl)-1-phenylpropane; and with a member selected from the group consisting of carbonyl bromide, phosgene and bis-chloroformic ester of said comonomer or said dihydric phenol and a diaryl carbonate.
 3. The process of claim 2 wherein said dihydric phenol is bisphenol-A.
 4. The copolycarbonate prepared in accordance with the process of claim
 2. 